Aromatic polyepoxide-modified oxyalkylated phenol-aldehyde resins and method of making same



United States Patent Oflice 2,854,427 Patented Sept. 30, 1958 2,854,427 AROMATIC POLYEPOXIDE-MODIFIED OXYAL- KYLATED PHENOL-ALDEHYDE RESINS AND METHOD OF MAKING SAME If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer or'mixture of polymer and monomer.

Melvin De Groote, St. Louis, and Kwan-Ting Shen, 5 Stated .another "K We use materials Brentwood, Mo., assignors to Petrolite Corporation, of the kind described, for example, 1n S. Patent Wilmington Del a corporation f Delaware 2,5 30,353, dated November 14, 1950. Said patent de- No Drawing. Original application March 20, 1953, Se- Scribes compounds havmg the general folmula rial No. 343,804. Divided and this application June 15, 1956, Serial No. 591,551

3 Claims. c1. 260-43) This application is a division of our co-pending apz R. plication Serial No. 343,804, filed March 20, 1953, now 2 abandoned.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in wherein R is an aliphatic hydrocarbon bridge, each processes or procedures particularly adapted for prep e ly has one of the Values 0 and and X is venting, breaking or resolving emulsions of the wateran alkyl radical containing from 1 t0 4 carbon atomsin-oil type and particularly petroleum emulsions. Our The Compounds having two oxifane rings are invention is also concerned with the application of such p unds of the following formula and cogenerically aschemical products or compounds in various other arts sociated compounds formed in their preparation:

0 i. H 0 o o-c- 0R1[R],.R1OC-(i C] 0Ri[RlR1O-C--C O H: H H H: H2 I H: H H:

and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The products of our invention are synthetic hydrophile products obtained by the reaction of certain oxyalkylated phenol-aldehyde resins, hereinafter described in detail, with certain phenolic polyepoxides, also hereinafter described in detail and cogenerically associated compounds formed in their preparation.

A particular embodiment of the products of our invention are synthetic hydropile products obtained by the reaction of the monoepoxide oxyalkylation derivatives of the reaction products of phenol-aldehyde resins derived from difunctional monohydric phenols and aldehydes having not over 8 carbon atoms, particularly, formaldehyde, in which the difunctional monohydric phenol residue is derived from a hydrocarbon substituted phenol,

with phenolic diepoxides of the following formula;

phenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or alde= hyde.

in which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom andaldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical v H H c. H H

the divalent 0 II radical, the divalent sulfone radical, and the divalent monosulfide radical S-, the divalent radical -CH SCH and the divalent disulfide radical --S--S-; and R 0 is the divalent radical obtained by the elimination of' a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, R, and R' represent a hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents either zero or 1, and n represents a whole number not greater than 3-. The above mentioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solvent-soluble. Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infus'ible resins. organic solvent means any of the usual organic solvents,

Reference to being soluble in an such as alcohols, ketones, esters, ethers, mixe d solvehts;

Reference to solubility is merely toditferentiate,

etc. from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with amine. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxy tetraethyleneglycol. a

The expression epoxy is not-usuallylimited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings, Hereinafter, the word epoxy, unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-

epoxide rings or oxirane rings in the alpha-omega position. This is adeparture, of course, from the standpoint of a strictly fbrma'lnomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2-3 ,4-diepoxybutane) Y ber of instances.

It well may be that even though the previously suggested formula represents the principal component, or components, of the result or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances watersoluble, in fact colloidally soluble.

Basic nitrogen atoms can be introduced into such derivatives by use of a reactant having both a nitrogen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil type, and also for that matter for numerous other purposes where surface-active materials are effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of mono-epoxides, in such manner that the derivatives so obtained have sufficient hydrophile character to meet at least the test set forth in U. S; Patent No. 2,499,368 dated March 7, 1950, to De Groote et al.' In said patent such test for emulsification-using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated derivatives obtained particularlyby use of ethylene oxide, propylene oxide, .etc., may not necessarily be xylenesoluble although they are xylene-soluble in a large num- If such compounds are not xylenesoluble the obvious chemicalequivalent, or equivalent chemical test, can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a I mixture to dissolve the appropriate product being exmolecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See

U. S. Patent No. 2,494,295, dated']anuary 10, 1950', to

Greenlee. The compounds here included are limited to the monomers or the low molal members of suchseries and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which'are' not resins and have certain solubility characteristics not inherent in resins.

To illustrate the products which represent the subject i ence manifest. :1 hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

matter of the present invention reference will be made I- to a reaction involving a mole of the oxyalkylating agent, i. e., the compound havingtwo oxirane rings and oxyalkylated resins as described. Proceeding with the example previously described itis obvious the reaction ratio of two moles of the resin to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

amined and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makes its pres- It is understood the reference in the Another peculiarity of the compounds herein described is that they may pass into a comparatively high molecular weight range and be effective for various purposes, not only for the resolution of petroleum emulsions but also for other industrial uses described in detail elsewhere. This characteristic may be related to the fact that the initial resin molecule, obtained in turn from two resin molecules combined by means of a polyepoxide as described, results in a fairly large molecule.

As previously pointed out, we have found that we can obtain effective compounds for the herein described purposes where surface-active materials are employed, whether it be for the resolution of petroleum emulsions H H (Oxyalkylated resin) in which the various characters have their prior significance. However, molal ratios may be varied as noted subsequently. 1 Such products must be soluble in suitable solvents such alkylene oxide.

as a non-oxygenated hydrocarbon solvent or an oxygenated hydrocarbon solvent or, for that matter, a mixture of the same 'With water. Needless to say,-after the-resin has been treated with a large amount of ethylene oxide the products are water soluble and may be 'soluble in an (oxyalkylated resin) or other uses, in which the oxyalkylated derivatives subjected to reaction with a polyepoxide may represent roughly two parts of the initial resin and 98% of the The word, oxyalkylated, is employed in this sense for the purpose of convenience in referring to the monoepoxide derivative only.

For purpose of convenience, what is said hereinafter will be divided into eight parts with Part 3, in turn,

being divided into three subdivisions.

acid solution. The purpose in this instance'is to differ-en V tiate from insoluble resinous materials, particularly those' resulting from cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly soluble in 5% acetic acid. For instance, the products freed from any tion of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with suitable phenol-aldehyde resins to be employed for reaction with the epoxides;

Part 5 is concerned with the oxyalkylation of the previously described phenol-aldehyde resins;

Part 6 is concerned with reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between two moles of a previously prepared oxyalkylated phenol-aldehyde resin as described and one mole of a polyepoxide so as to yield a new and larger oxyalkylated resin molecule.

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. Is is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co-generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers are available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, We have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers aresatisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dirnethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfurcontaining compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. A number of problems are involved in attempting to produce these materials free from cogeneric materials of related composition. For a discussion of these difficulties, reference is made to U. S. Patent No. 2,819,212, beginning at column 7, line 21.

PART 3 Subdivision A The preparations of the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit, aforementioned U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are

included for purpose of illustration. compounds are described in the two patents just men- These particular particularly the aforementioned U. S. Patents Nos. 2,575,- 558 and 2,582,985.

tioned. In light of the aforementioned U. S. Patent No.

TABLEI Ex- Patent ample Dlphenol Diglycidyl ether refernumber enoe 1A CH1(C|H4OH)1 Dl(epoxypropoxyphenylmethane"; 2, 506,486 2A CHJCH(C|H4OH)|-; Di(epoxypropoxyphenylgmethylrnethane... 2, 506,486 3A (OH:):C(C4H4OH); Di(epoxypropoxyphenyl)dimethylmethane 2,506,486 4A CzHsC(CH:)(CaHcH):---- Di(epoxypropoxyphenylethylmethyl methane 2,506,486 5A :H1)zC(O|H40H)1 Di(epoxypropoxyphenyl diethylmethane 2, 506,486 6A CH;CEC|H1)(CH4OH):.-.. D1(epoxypropoxyphenyl)methylpropy1methane. 2, 506,486 7A OHaC CBHL)(COH6OH)|-- Di(epoxypropoxyphenyl)methylphenylmethane.. 2,506,486 8A CIHBC(CH5)(O0HOH)1.-- Di(opoxypropoxyphenyl)ethylphenylrnethane---. 2,506,486 9A C: 1C(CH;)(G H40H)| Dl(epoxypropoxyphenyDprOpylphenYImethane 2, 506,486 10A O4 lC(O||H5)(CBHl0H)L-- Dl(epoxypropoxyphenyl)butylpheny methane- 2, 506,486 8C6H4)OH(CflHloH)L--- Di(epoxypropoxyphonyl)tolylmethane 2,506,486 12A (CH|C$H4)C(CH3)(CIHOH)1 Di(epoxypropoxyphenyl)tolylmethylmethane 2,506,486 13A"--. Dllfiydroxy diphenyl 4,4'-bis(2,3-epoxypropoxy)dlpllenyl 2,530,353 :)C(C4Hs.CaHaOH)1 2,2-bis(4-(2,3-epoxypropoxy)2-t0rtlarybutyl phenyDpropane..- 2,530,353

Subdivision B As to the preparation of low-molal polymeric epoxides 2,575,558, the following reference to the formula therein provided one still bears examples can be specified by or mixtures reference is made to numerous patents and 111 mlnd 11315111 essence all ovef'slmphficatlon- TABLE II I C 0-0 0R1-[R].R10CC-C OR1-[R]..-R O-CCC H H: g H: H

(in which the characters have their previous significance) Example R 0 from HRIOH -R-- n n Remarks number B1 Hydroxy benzene CH; 1 0,1,2 Phenol known as bishenol A. Low I polymeric mixture a ut 86 or more C where n=0, remainder largely where 4 'n=1, some where n=2.

B2 do OH; 1 0, 1, 2 Phenol known as bis-phenol B. See note regarding B1 above. 6H, 511.

B3 Orthobutylphenol CH; 1 0,1,2 Even though 1: is preferably 0, yet the I usual reaction product might well eon- -O tain materials where n is 1, or to a l lesser degree 2. CH;

B4 Orthoamylphenol in, 1 0,1,2 Do.

Orthooctylphenol in, 1 0,1,2 Do.

I CH;

B6 Orthononylphenol EH; 1 0,1,2 Do.

B7 Orthododecylphenol CH; 1 0,1,2 Do.

Ba MRfBM'PWfl CH; 1 0,1,2 See prior note. This phenol used as initial material is known as bls-phenol C. For other suitable bis-phenols see 5H U. S. Patent 2,564,191.

TABLE 11 (continued) Example R1O from HR H R- n n Remarks number B9 Metacresol .14-; CH; 1 0,1,2 See prior note.

| OH; (EH3 1310...-.. Dibutyl (ortho-para) phenol. lg 1 0,1,2 Do.

B11 Diamyl (ortho-pnra.) phenol. :61 '1 0,1,2 Do.

B12 Dioetyl (ortho-pa'ra) phenol. 1g 1 0,1,2 Do.

B13 Dinonyl (ortho-para) phenol. 1g 1 0,1,2 Do.

B14 Diamyl (orthopara) phenoL EC! 1 0,1,2 Do. I

B15 do g 1 0,1,2 Do.

1316.-.... Hydroxy benzene (i) 1 0,1,2 Do.

B17 Dlamyl phenol (ortho-para). -SS-' 1 0,1,2 Do.

B18, ..do s 1 o, 1, 2 Do. 1819..-... Dibutylphenol(orthd-para). 15 g 1 0,1,2 Do.

' H H B20 do H H 1 0,1,2 Do.

. C H H B21 Dinonylphenol(ortho-para). lg 161 1 0,1,2 Do.

1322 Hydroxy benzene"; C") 1 0,1,2 Do.

B23 do None 0 0,1,2 Do.

Orthoisopropyl phenol OH: 1 0,1,2 See prior note. (Asto preparation 01 4,45

I isopropylidene bis-(2-isopropylphenol) 3 see U. S. Patent No. 2,482,748, dated 1 Sept. 27, 1949, to Dietzler.) CH: H B25 Paraoctyl phenol CH2-SCH2 1 0,1,2 Seepriornote. (As to preparationo'tthd '1 phenol sulfide see U. S. Patent No.

2,488,134, dated Nov. 15, 1949, to Mikeska et a1.)

1326 Hydroxybenzene CH: 1 0,1,2 seepriornote. (As to preparationoIthephenol sulfide see U. S. Patent No. 2,526,545.)

SubdivisionC For purpose of illustration attention is directed to nu- Th 168 h ve been limited lar 61 to those merous other diphenols which can be readily converted to in wliic h l ieiz i no di valent linking radicil as in the a Suitable polyepoxlde 9 particularly diepoxide case of diphenyl compounds, or where the linking radical 1 d t th a1 h l is derived from a ketone or aldehyde, particularly a kesprevlous y Pomt? e P may be tone. Needless to say, the same procedure is employed Stltuted, me substltuent Q P In turn y be a M in converting diphenyl into a diglycidyl ether regardless g p Such a thfi phenyl, group or cyclohexyl group as in of the nature of the bond between the two phenolic nuclei. the instance of cyclohexylphenol or phenylphenol. Such 11 substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

cm L r 110% 803 i Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohyd-rin, etc.

Other samples include:

RlfiEQRI I is wherein R is a substituent selected from the class con- See U. S. Patent No. 2,503,196.

wherein R is a member of thegroup consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

-wherein R is a substituent selected from theclass con sisting of secondary butyl and tertiary butyl groups and R; is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbonatoms. See U. S. Patent No. 2,515,907.

m0 0,110.0 owmiojtn GIHHUCHPQCIHH in which the C;H groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

C0111: CeHu See U. S. Patent No. 2,285,563.

CHrE-CH;

Ha AIR-CH:

CH: H CH ,sisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl,..aryl, aralkyl, and alkarylgroups.

U. S. Patent No. 2,515,906.

0H 0: H on See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

CIHH (EIHH See US. Patent No. 2,331,448. I

As to descriptions of various suitable phenolsulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766 2,244,021, -and 2,195,539. a

13 As to sulfones, see U. S. Patent No. 2,122,958. As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as Alkyl lkyl Al yl Alkyl in which R is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radi- See U. 3. Patent No.

OH CH3 CH5 OH in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and-R each preferably contains 3 to about 10carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U. S. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. Patents: Nos. 2,499,365, 2,499,366 and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents described phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atom also being very satisfactory. The increased cost of the C and C "carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol mayhave as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphe'nol and octadecylphenol, reference in each intance being to the difunctional phenol, such as the drthoor para-substituted phenol or a mixture of the same. Such resins are described also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature, for instance, it has been stated that the composition is approximated in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol'nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

In the aboveformula the aldehyde employed in the resin manufacture is formaldehyde. Actually, some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. The resin unit can be exemplified thus:

on on 1 on RIII RHI,

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially;- For 15 purpose of convenience suitable resins are characterized in the following table:

TABLE 111 M01. wt. Ex- R of resin ample R Position derived n molecule number of R from- (based on n+2) Tertiary butyl Para Formal- 3.5 882.5

dehyde Secondary butyl. Ortho--. do 3. 5 882. 5 Cyclohexyl Para do 3. 5 1, 025. 5 Tertiary amy do do 3. 5 959. 5 Mixed secondary Ortho--- .do 3.5 805.5

and tertiary amyl. Propyl Para .do 3.5 805. Tertiary hexyl" do do 3. 5 1, 036. Octyl dn do 3. 5 1.190. Nonyl .dodo. 3. 5 1.267. pe l (in (in 8. 5 1, 344. Dodecy do do 3. 5 1, 498. Tertiary butyl do Agetglde- 3.5 945.

. y e Tertiary amyl -do.. .do 3.5 1,022. Nonyl d o 3. 5 1. 330. Tertiary butyl do.. Butyral- 3.5 f 1,071.

dehyde. t Tertiary amy .do do 3. 5 1. 148. Non do do 3. 5 1, 456. Tertiary butyl do. Propion- 3. 5 1.008.

Tertiary amy 3. 5 1, 085. N nyl 3.5 1,393. Tertiary butyl 4. 2 996.

Tertiary amyl 4.2 1, 083. N onyl 4. 2 l, 430. Tertiary butyl 4. 8 1. 094. Tertiary amyl 4. 8 1, 189. Nonyl 4. 8 1, 570. Tertiary amyl 1.5 604. Oyclohexy 1. 5 646. Hexyl 1. 5 653. do 1. 5 688.

31a OetyL- 1. 5 786. m Nonyl 1. 5 s35.

- 33a Octyl 2.0 986.

34a Nonyl 2. 0 I 1, 028. 35a Amyl 2. 0 860. 36 Buty 2.0 636.

37 .Amyl. 2.0 692. 38 Beg 2.0 1 748. 39a Cy ohexyl 2.0 r 740.

PART 5 There have been issued a substantial number of patents which give detailed description of the preparation of oxyalkylated derivatives of resins'of the kind previously described. For example, see U. S. Patents 2,499,365,

2,499,366, 2,499,367, 2,499,368, and 2,499,370, March 7, 1950, to De Groote and Keiser.

More specifically, a number of other patents have appeared in which the oxyethylation step is given with conall dated siderable detail. See, for example, U. S. Patents 2,581,-

376, 2,581,377, 2,581,378, 2,581,379, 2,581,380, and 2,581,381, all dated January 8, 1952, to De Groote and Keiser. As to further examples see U. S. Patent 2,602,- 052, dated July 1, 1952, to De Groote.

The oxypropylation or, for that matter, the treatment 16 ready described in detail in the patent literature, we are referring to the tables beginning in column 21 of U. S. Patent 2,581,376 and extending through column 36. We have simply numbered these products beginning with lb, allotting, of course, five numbers to each table beginning with the first table. For convenience these sixteen tables are summarized in the following table:

TABLE IV 501- Eth- Exam- Phenol Aldehyde vent, Resin, ylene pleNo. s. lbs. oxide,

lbs

Formaldehyde.-. do

N0ra.-For ease of comparison blanks ap r in the aim a table wherev blanks appear in pieviously mentione t ables in U. 8. Patent 2,581,376.

17 Oxypropylated derivatives comparable to 1b through 80b as described above can readily be obtained by substituting a molar equivalent amount of propylene oxide,

is cluded, the descriptions of which appear in detail in said aforementioned U. S. Patent 2,577,081 to De Groote and Keise'r.

TABLE VI See U. S. Pat.

Ethylene Propylene Flake Ex. No. 1 Point Resin used Resin, oxide, oxide, Weight caustic Ex. No. on lbs. lbs. lbs. of xylene soda,

in graph ounces above on patent above patent Teri;i amylphenol formaldehyde. o

i. e., 56 lbs. of propylene oxide, for example, for each 44 lbs. of ethylene oxide. We have prepared such a similar series but for sake of brevity only a few will be included for purposes of illustration.

As an illustration of oxypropylated resins involving the use of both ethylene and propylene oxide, reference is made to the aforementioned U. S. Patent 2,557,081, dated June 19, 1951, to De Groote and Keiser. 'The last table in column 28 of said patent describes in detail the preparation of a series of oxyalkylated resins in which both propylene and ethylene oxide are employed. Simply by way of illustration a series of 27 compounds are in- Note the first series of nine compounds, 1d through 9d, were prepared with .a propylene oxide first and then ethylene oxide. The second 9, 10d through 18d inclusive, were prepared using ethylene oxide first and then propylene oxide, and the last 9, 19d through 27d, were prepared by random oxyalkylation, i. e., using a mixture of the two oxides.

In thepreparation of the resins our preference is to use hydrocarbon substituted phenols, particularly para-substituted, .in which the substituted radical R contains 4 to 18 carbon atoms and particularly 4 to 14 carbon atoms. The amount of alkylene oxide introduced may be comparatively large in comparison to the initial resin. For instance, there may be as much as 50 parts by weight of an oxide or mixed oxides used for each part by weight of resin employed.

It will be noted that the various resins referred to in the aforementioned U. S; Patent 2,499,370 are substantially the same type of materials as referred to in Table III. For instance, resin 2a of the table is substantially the same as 2a of the patent; resin 19a of the table is substantially-the same as 34a of the patent; and resin 37a of the table is the same as 311 of the patent.

In reaction with polyepoxides, and particularly diepoxides, alarge number of the previously described oxyalkylated resins have been employed. For convenience, the following list is selected indicating the previously described compounds and their molecular weights. Such resins are generally employed as a 50% solution andthe polyepoxide employed is a 50% solution, usually both reactants being dissolved in xylene and sufiicient sodium methylate added to act as a catalyst, for instance, 1 to 2%.

TABLE VII Example number Molecular Example number Molecular weight weight PART 6 As previously stated, the final stage reactions involve two moles of an oxyalkylated phenol-aldehyde resin of the kind previously described and one mole of a diglycidyl ether as specified. The reaction is, essentially an oxyalkylation reaction and thus may be considered as merely a continuance of the previous oxyalkylation reaction. The previous oxyalkylation reaction involved a monoepoxide as differentiated from a polyepoxide and particularly a diepoxide. The reactions take place in substantially the same way, i. e., by the opportunity to react at somewhere above the boiling point of water and below the point of decomposition, for example,

130-185 C. in the presence of a small amount of alkaline catalyst. Since the polyepoxide is non-volatile as compared, for example, with ethylene oxide, the reaction is comparatively simple. Purely from .a mechanical standpoint it is a matter of convenience to conduct both classes of reactions in the same equipment. In other words, after the phenol-aldehyde resin has been reacted with ethylene oxide, propylene oxide or the like, it is subsequently reacted with a polyepoxide. The polyepoxide reaction can be conducted in an ordinary reaction vessel such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described-in a number of patents, as for example, U. S. Patent No. 2,499,365. One can use a variety of catalysts in connection with the polyepoxide of the same class employed with monoepoxide. In fact, the reaction will go at an extremely slow rate without any catalyst at all. The usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chlorides. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. For practical purposes, it is best to use the same catalyst as is used in the initial oxyalkylation step and in many cases there is sutficient residual catalyst to serve for the reaction involving the second oxyalkylation step, i. e., the polyepoxide. For this reason, we have preferred to use a small amount of finely divided caustic soda or sodium methylate as the initial catalyst and also the catalyst in the second stage. The amount generally employed is 1, 2, or 3% of these alkaline catalysts.

Actually, the reactions of polyepoxides with various resin materials have been thoroughly described in the literature and the procedure is, for all purposes, the same as with glycide which has been described previously.

It goes without saying that the reaction involving the polyepoxide can be conducted in the same manner as the monoepoxide as far as the presence of an inert solvent is concerned, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent'such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The solvent soselccted should be one which, of course, is suitable in the oxyalkylation step involving the monoepoxidcs described subsequently. The solvent selected may depend on the ability to remove it by subsequent distillation if required. Here again it has been our preference to have a solvent present in the oxyalkylation involving the initial stage and permitting the solvent to remain. .The amount of solvent may be insignificant, depending Whether or not exhaustive oxyalkylation isemployed. However, since the oxyalkylated phenol-aldehyde resins are almost invariably liquids there is -no need for the presence of a solvent as when oxyalkylation involves a solid which may be rather high melting. Thus, it is immaterial whether there is solvent present or not and it is immaterial whether solvent was added in the first stage of oxyalkylation or not, and also it is immaterial whether there was solvent present in the second stage of oxyalkylation or not. The advantage of the presence of solvent is that sometimes it is a convenient way of controlling the reaction temperature and thus in the subsequent examples we have added sufiicient xylene so as to produce a mixture which boils somewhere in the neighborhood of to C. and removes xylene so as to bring the boiling point of the mixture to about 140 C. during part of the reaction and subsequently removing more xylene so that the mixture refluxed at somewhere between to C.

' Example Is The oxyalkylated resin employed was the one previously identified as 2b, having a molecular weight of 2169; the amount employed was 217 grams. The resin was dissolved in approximately an equal weight of xylene. The mixture was heated to just short of the boiling point of water, i. e., a little below 100 C. Approximately one-half percent of sodium methylate was added, or, more exactly, 1.1 grams. The stirring was continued until there was a solution or distribution of the catalyst. The mixture was heated to a little past 100 C. and left at this temperature while 17 grams of the diepoxide (previously identified as 3A), dissolved in an equal weight of xylene, were added. After the diepoxide was added the temperature was permitted to rise to approximately 107 C. The time required to add the diepoxide was approximately one-half hour. The temperature rose in this period to about 125 C. The temperature rise was controlled by allowing the xylene to reflux over and to separate out the xylene by a phase separating trap. In any event, the temperature was raised shortly to 138l40 C. and allowed to reflux at this temperature for almost three hours. Tests indicated that the reaction was complete at the end of this time; in fact, it probably was complete at a considerably earlier stage. The xylene which had been separated out was returned to the mixture so that the reaction mass at the end of the procedure represented about 50% reaction product and 50% solvent. The procedure employed is, of course, simple in light of what has been said previously; in fact, it corresponds to the usual procedure employed in connection with an oxyalkylating agent such as glycide, i. e., a non-volatile oxyalkylating agent. At the end of the reaction period the mass obtained was a dark, viscous mixture. It could be bleached, of course, by use of charcoal, filtering earths, or the like.

Various examples obtained in substantially the same manner as employed are described in the following table:

TABLE VIII Oxy- Catalyst Time of Max. Ex. alkyl- Amt, Diepox- Amt., (N aOGHa), Xylene, Molar reaetio temp, Color and physical state No. ate d gms. ide used gms. grams gms. ratio hrs. 0.

resin 217 3A 17 1.1 234 2:1 3 140 Dark, viscous mass. 460 3A 17 2.4 477 2:1 4 145 Do. 247 3A 17 1.3 264 2:1 3 150 D0. 609 3A 17 3. 1 626 2:1 4 148 Do. 249 3A 17 1. 3 266 2: 1 2. 5 150 Do. 402 3A 17 2. 419 2: 1 4 146 D0. 708 8A 17 3. 6 725 2: 1 5 152 Do. 192 3A 17 1. 0 209 2:1 2. 5 142 Do. 319 3A 17 1. 6 336 2:1 3 147 Do. 249 3A 17 1. 2 250. 7 2; 1 3 155 Do. 217 B1 27.5 1.2 244.5 2:1 3.5 145 D0. 460 B1 17 2. 4 487.5 2:1 4 150 Do. 247 B1 17 1. a 274. 5 2:1 4 152 Do. 609 B1 17 3. 1 636. 5 2:1 5 158 Do. 249 B1 17 1. 3 276. 5 2: 1 4 146 Do. 402 B1 17 1.2 429.5 2:1 5 150 Do. 708 B1 17 2. 6 735. 5 2: 1 5 152 Do. 192 B1 17 1.0 219.5 2:1 3.5 148 1 Do. 319 B1 17 1. 7 346. 5 2:1 4 150 D0. 249 B1, 2.8 1. 2 251.8 2:1 3 152 Do.

TABLE IX The materials of our invention, when employed as treatmg or demulsifying agents, are used in the conven- P b m tional way, well known to the art, described, for example,

IO 9, e oxyalkylated molecular Amount of Amount of in Patent2 ,626,929, dated January 27, 19 53, Part 3, and Ex. N0. resin wt. of product, solvent, reference 1s made thereto for a description of convengTams grams tional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process 4,680 4,680 2,340 essentially involving introducing a small amount of de- 9, 540 4,770 2,885 mulsifier mto a large amount of emulsion with adequate 3 238 gig? 31%; admixture with or without the application of heat, and

5, 320 5, 3:;0 2,650 allowing the mixture to stratify. 2: $12 8 mg As noted above, the products herein described may 4,120 g, 133 gg be used not only in diluted form, but also may be used 8: 1' 8 :3 508 35 admixed with some other chemical demulsifier. A mix- $1338 3,223 ture which illustrates such combination is the following: 5 5:490 2:745 Oxyalkylated derivative, for example, the product of %.;38 2.238 Example 2e, 20%; 590 590 15,3 A cyilfohexylamine salt of a polypropylated napthalene 14,710 7,355 3, 7 m

4,390 4,385 2,190 40 2 2 (mm i 1 6,930 6,930 3,465 ammonium sat o a po ypropylated napthalene 370 5,040 2, 520 monosulfomc acld, 24%;

PART 7 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or evenl to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of our invention when employed as demulsifying agents.

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 8 wherein R and R" are alkyl groups.

It is not necessary to point out that after reaction with a reactant of the kind described which introduces a basic nitrogen atom that the resultant product can be employed for the resolution of emulsions of the water-in! oil type as described in Part 7, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 6 preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes; as ingredients in insecticide composition; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. I

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherizanon, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose-of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type; as additives in the flotation of ores, and at times as aids in chemical reactions in so far that demulsification is I produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoarners, asphalt additives, and at times even in the resolution of oil-in-water emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent, is:

l. The method of reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a phenolic polyepoxide containing at least two 1,2-epoxy rings free from reactive functional groups other than epoxy and hydroxyl groups, and co-generically associated compounds formed in the preparation of said polyepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class consisting of (a) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (b) compounds containing a radical in which two phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical 4, the divalent radical CH SCH and the divalent disulfide radical 24 S-S; said phenolic portion. of the diepoxide being obtained from a phenol of the structure III RI! I 'products derived by oxyalkylation of (aa) an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (bb) a fusible, organic solventsoluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated hydrocarbon radical having not more than 24 carbon atoms and substituted in the 2, 4, 6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O),,, in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to reactant (B) being in the proportion of two moles of (A) and one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. The product obtained by the method defined in claim 1.

3. The method of reacting (A) an oxyalkylated phenol-aldehyde resin containing a plurality of active hydrogen atoms, and (B) a compound consisting essentially of the following formula HaCCHCH2-OO C(CHs): z

stantial absence of trifunctional phenols; said phenol being of the formula in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to 120; v

with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus, and that the resin by weight represent at least 2% of the oxyalkylated derivative; the ratio of reactant (A) to retactant (B) being in the proportion of two moles of (A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and solids melting below the point of pyrolysis; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

References Cited in the file of this patent UNITED STATES PATENTS 2,498,656 De Groote et a1. Feb. 28, 1950 2,521,911 Greenlee Sept. 12, 1950 2,723,241 De Groote et a1. Nov. 8, 1955 v 

1. THE METHOD OF REACTING (A) AN OXYALKYLATED PHENOL-ALDEHYDE RESIN CONTAINING A PLURALITY OF ACTIVE HYDROGEN ATOMS, AND (B) A PHENOLIC POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS FREE FROM REACTIVE FUNCTIONAL GROUPS OTHER THAN EPOXY AND HYDROXYL GROUPS, AND CO-GENRICALLY ASSOCIATED COMPOUNDS FORMED IN THE PREPARATION OF SAID POLYESPOXIDES; SAID EPOXIDES BEING MONOMERS AND LOW MOLAL POLYMERS NOT EXCEEDING THE TETRAMERS; SAID EPOXIDES BEING SELECTED FROM THE CLASS CONSISTING OF (A) COMPOUNDS WHERE THE PHENOLIC NUCLEI ARE DIRECTLY JOINED WITHOUT AN INTERVENING BRIDGE RADICAL, AND NOLIC NUCLEI ARE JOINED BY A DIVALENT RADICAL SELECTED FROM THE CLASS CONSISTING OF KETONE RESIDUES FORMED BY THE THE CLASS CONSISTING OF KETONE RESIDUES FORMED BY THE ELIMINATION OF THE KETONIC OXGEN ATOM, AND ALDEHYDE RESIDUES OBTAINED BY THE ELIMINATION OF THE ALDEHYDE OXYGEN ATOM, THE DIVALENT RADICAL 